title: O-atom scrambling in the aqueous isomerization of pernitrous acid.
abstract: Raman spectroscopy has been used to determine the isotopic distribution of oxygen during the isomerization of pernitrous acid to nitrate in 18OH2. Decomposition of unlabeled pernitrous acid in carbon-dioxide-free phosphate-buffered solutions of 18OH2 at pH 6.8 results in the incorporation of 13 +/- 1% 18O into the nitrate product with no detectable double-isotopic incorporation and 83% of the product having complete retention of its oxygen atoms. The mechanistic implications of this are contrasted for three frequently considered pathways for peroxide bond cleavage and it is concluded that the results are most consistent with the formation of reactive intermediate which can either rearrange or undergo hydrolytic O-atom exchange with water.
authors.affiliation: Department of Chemistry, University of Wyoming, Laramie 82071-3838, USA.
authors.forename: D S
authors.initials: DS
authors.lastname: Bohle
authors.forename: B
authors.initials: B
authors.lastname: Hansert
mesh_terms: D005609:Free Radicals / Q000378:metabolism; D007536:Isomerism; D009566:Nitrates / Q000378:metabolism*; D009573:Nitrites / Q000378:metabolism; D009608:Nitrous Acid / Q000737:chemistry*; D010100:Oxygen / Q000378:metabolism; D010103:Oxygen Isotopes; D030421:Peroxynitrous Acid; D000644:Quaternary Ammonium Compounds / Q000378:metabolism; D013059:Spectrum Analysis, Raman; D013816:Thermodynamics; D014867:Water / Q000378:metabolism
chemical_list: D005609:Free Radicals; D009566:Nitrates; D009573:Nitrites; D010103:Oxygen Isotopes; D000644:Quaternary Ammonium Compounds; C113914:tetramethylammonium peroxynitrite; D014867:Water; D030421:Peroxynitrous Acid; D010100:Oxygen; D009608:Nitrous Acid